Sensor for the Direct Detection of Iodine
20190302078 ยท 2019-10-03
Inventors
Cpc classification
International classification
G01N33/00
PHYSICS
Abstract
An all solid-state, MOF-, zeolite-, or activated carbon-based electrical readout sensor with a long-lived signal can be tuned specifically for real-time sensing of iodine gas in ambient conditions. The sensor may be of use in nuclear accident scenarios for first responders and/or as process sensors in advanced nuclear fuel recycling.
Claims
1. An iodine sensor, comprising: an insulating substrate; an array of interdigitated electrodes disposed on the substrate; a coating, comprising an iodine-capture material, disposed on the array of interdigitated electrode pairs; and a frequency response analyzer for measuring the impedance response of the coating when an iodine species is absorbed in the iodine-capture material and an alternating voltage is applied to the pairs of interdigitated electrodes.
2. The iodine sensor of claim 1, wherein the iodine-capture material comprises a MOF material.
3. The iodine sensor of claim 2, wherein the MOF material comprises a zeolitic imidazolate framework material.
4. The iodine sensor of claim 3, wherein the zeolitic imidazolate framework material comprises ZIF-8.
5. The iodine sensor of claim 1, wherein the iodine-capture material comprises a zeolite or activated carbon.
6. The iodine sensor of claim 5, wherein the zeolite comprises silver-mordenite.
7. The iodine sensor of claim 1, wherein the iodine species comprises an iodine-containing gas or aerosol.
8. The iodine sensor of claim 1, wherein the iodine species comprises I.sub.2, CH.sub.3I, CH.sub.2I.sub.2, C.sub.3H.sub.7I, CH.sub.2CCII, HIO.sub.3, IO, IO.sub.2, I.sub.2O.sub.2, IONO.sub.2, ICI, HI, or HOI.
9. The iodine sensor of claim 1, wherein the coating has a thickness of less than 100 m.
10. The iodine sensor of claim 9, wherein the coating has a thickness of less than 10 m.
11. The iodine sensor of claim 10, wherein the coating has a thickness of less than 1 m.
12. The iodine sensor of claim 1, wherein the alternating voltage has a frequency between 10 mHz and 1 MHz.
13. The iodine sensor of claim 1, further comprising a high impedance interface connected in series with the frequency response analyzer.
14. The iodine sensor of claim 1, wherein the sensor has an operating temperature of less than 70 C.
15. The iodine sensor of claim 1, wherein the iodine sensor is an integrating sensor.
16. An iodine sensor, comprising: an insulating substrate; an array of interdigitated electrodes disposed on the substrate; a coating, comprising an iodine-capture material, disposed on the array of interdigitated electrode pairs; and a meter for measuring a change in conductivity of the coating when an iodine species is absorbed in the iodine-capture material and a constant current, constant voltage, or swept voltage is applied to the pairs of interdigitated electrodes.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0013] The detailed description will refer to the following drawings, wherein like elements are referred to by like numbers.
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DETAILED DESCRIPTION OF THE INVENTION
[0022] The present invention is directed to an iodine sensor comprising a metal-organic framework (MOF), zeolite, or activated charcoal iodine-capture material disposed on interdigitated electrodes (IDEs). MOFs are hybrid organic-inorganic materials composed of a metal ion or cluster of metal ions coordinated to organic ligands, or linkers, to provide a nanoporous framework. For example, the MOF can comprise a zeolitic imidazolate framework (ZIF) material. ZIFs are composed of tetrahedrally-coordinated transition metal ions (e.g. Fe, Co, Cu, Zn) connected by imidazolate linkers and are topologically isomorphic with zeolites. ZIFs have high porosity, are resistance to thermal changes, and have robust chemical stability. Zeolites are fully inorganic, nanoporous aluminosilicate materials. For example, the zeolite can be a silver-mordenite (Ag-MOR) or other silver-exchanged zeolite. Activated carbons are fully organic forms of carbon that are processed to have small, low-volume pores with increased surface area for gas absorption. All of these materials can capture iodine and other organoiodide species, such as CH.sub.3I, CH.sub.2I.sub.2, C.sub.3H.sub.7I, CH.sub.2CCII, HIO.sub.3, IO, IO.sub.2, I.sub.2O.sub.2, IONO.sub.2, ICI, HI, and HOI. These species can be present as gases or aerosolized particulates.
[0023] The invention can further comprise a frequency response analyzer for measuring the impedance response of the coating when an AC voltage is applied to the IDEs. The IDEs comprise an array of interlocking comb-shaped pairs of metallic electrodes deposited on the surface of an insulating substrate. Impedance spectroscopy measures the electrical impedance of the coated IDEs over a range of frequencies. The impedance can be related to the capacitance and conductivity of the iodine-capture material. When an alternating voltage is applied to the IDE, some energy is stored by the capacitance, and some is dissipated by the resistance effects. Therefore, the resulting current will exhibit a phase lag. The capacitance effect is known as the permittivity (or dielectric constant), and the resistive effect as dielectric loss. In materials where the dielectric loss is very small and the permittivity is large, a high impedance interface can be connected in series with the frequency response analyzer to provide a more accurate impedance measurement. The high impedance interface enables a reference measurement to be obtained on precision internal reference capacitors which are automatically substituted for the sample; a second measurement is made, this time on the sample itself. The two results are used to derive an accurate measurement of the permittivity of the sensing materalin effect, the first measurement is used to eliminate the effects of extraneous capacitance.
[0024] Alternatively, the invention can comprise a meter for measuring the change in conductivity of the coating when an iodine species is absorbed in the iodine-capture material when a constant current, constant voltage, or swept voltage is applied to the pairs of interdigitated electrodes.
[0025] As an example of the invention, a sensor was fabricated comprising ZIF-8 coated on platinum IDEs on a glass substrate. ZIF-8 is a MOF comprised of zinc ions coordinated by four imidazolate rings, having the composition Zn(MeIM).sub.2. See K. S. Park et al., Proc. Nat. Acad. Sci. 103(27), 10186 (2006). Previous work has shown that the ZIF-8 is highly selective to I.sub.2 gas through strong binding inside the framework's -cage, where guest-framework interactions occur between the highly polarizable I.sub.2 molecules and the 2-methylimidazole ligands. See D. F. Sava et al., J. Am. Chem. Soc. 133, 12398 (2011); and J. T. Hughes et al., J. Am. Chem. Soc. 135, 16256 (2013). Further, ZIF-8 is inexpensive and commercially available in kilogram quantities, making it an economically attractive choice for a commercial I.sub.2 sensor. Practically, ZIF-8 is hydrophobic compared to other MOFs known to selectively absorb I.sub.2. This hydrophobicity enables a stable background reading before I.sub.2 is introduced. Furthermore, the pore size opening of the ZIF-8 framework closely approximates that of the I.sub.2 molecule (head-in) and therefore can be consider optimum for the size electivity of the gas molecule.
[0026] The electrodes comprised 125 pairs of platinum electrodes 250 nm thick and 10 m wide with a 10 m spacing between electrodes. Prior to coating with the ZIF-8 material, the IDEs were rinsed with methanol, dried under nitrogen, heated to 70 C. in air for 30 minutes, and cooled to room temperature. The IDEs were then coated with ZIF-8 using a dropcasting technique. 200 mg of ZIF-8 (Basolite Z1200, Sigma-Aldrich) was mixed with 2 mL methanol. The mixture was sealed and magnetically stirred vigorously for 30 minutes, after which 25 L was pipetted onto the active area of the IDE. The IDE was allowed to dry at room temperature for 10 minutes, followed by heating at 70 C. on a hotplate in air for 30 minutes. This procedure consistently deposited 1.870.13 mg of ZIF-8 onto the IDE with a film thickness on the order of 35 m. The sensors were exposed to I.sub.2 at 25, 40, or 70 C. for 30 minutes, followed by heating at 70 C. in air to minimize I.sub.2 simply absorbed to the sensor surface. I.sub.2 vapor pressures at 25, 40, and 70 C. are 16.8, 35.2, and 124 kPa, respectively. Photographs of the sensors at each point in this process are shown in
[0027] Impedance spectra were recorded with a frequency spectrum analyzer connected in series with a high impedance interface, utilizing internal reference capacitors for measurements, as described above. The high input impedance of this system enabled measurement of impedances up to 10.sup.14. Impedance spectra were recorded at 0 V DC and 100 mV (RMS) AC over 1 MHz-10 mHz.
Testing of MOF-Based Sensor
[0028] The MOF-based sensor was tested under a variety of experimental conditions to examine the effects of environmental conditions on response and selectivity. These included, studying the effect of: (1) variable temperature and time of exposure to iodine gas on the sensor's response, (2) competing gas (air component) molecules on selectivity to iodine, and (3) the structural integrity of the MOF and the overall sensor after exposure to these conditions. By analyzing the resultant electrical response (impedance spectroscopy responses) under varying experimental conditions, the strength and durability of the electrical readout signal from this MOF-based sensor can be determined.
[0029] An example impedance response of these sensors is presented in
[0030] The impedance behavior of this system was modeled using an equivalent circuit to help separate the response of the glass substrate from that of the ZIF-8. This equivalent circuit, shown in
Sensor Response as a Function of Temperature
[0031] The percent change in R.sub.Z and C.sub.Z were determined for sensors exposed to I.sub.2 at 25, 40, and 70 C. Additionally, two control samples were run at each temperature: (1) an uncoated sensor exposed to I.sub.2 and (2) a ZIF-8 coated sensor thermally treated in the absence of I.sub.2. These data are summarized in
[0032]
[0033] The capacitive response of the sensor, presented in
[0034] The most profound changes in response are seen in terms of the ZIF-8 resistance, R.sub.Z. Changes in R.sub.Z are plotted in
[0035] The variability of R.sub.Z at low temperatures is significant; at 25 and 40 C., uncertainty was 34% and 60%, respectively, of the reported value. This uncertainty is dominated by experimental reproducibility; contributions from impedance accuracy (0.2%) and fitting uncertainty for R.sub.Z (3-6%) are minimal. It is likely that the exact distribution of I.sub.2 in the sensor, in terms of both molecular location in the ZIF-8 (sodalite cages vs. absorbed to surface) and penetration depth relative to the Pt electrodes, greatly influences the recorded values of R.sub.Z. At 70 C., uncertainty is still 60%, though this uncertainty is insignificant compared to the 5 orders of magnitude change in response. However, the evaluation of R.sub.Z unequivocally demonstrates that sorption of I.sub.2 into ZIF-8 profoundly changes the impedance response at high I.sub.2 loadings.
MOF Structural Analysis and Sensor Response after Exposure to Iodine
[0036] To ascertain changes in ZIF-8 crystal structure upon I.sub.2 sorption, powder X-ray diffraction (XRD) was performed on uncoated, ZIF-8 coated, and ZIF-8 coated and I.sub.2 exposed samples. The resulting data is plotted in
[0037] As shown in
[0038] It has been previously shown that amorphization of the ZIF-8 structure enhances I.sub.2 capture and retention without destruction of the local structure surrounding the captured I.sub.2. See K. Chapman et al., J. Amer. Chem. Soc. 133, 18583 (2011); and T. Bennett et al., Chem. Eur. J. 19, 7049 (2013). Attempts to remove I.sub.2 from the 70 C. samples using moderate vacuum (<1 mTorr) under heat (70 C.) were only successful in removing 28 wt % of ZIF-8 in I.sub.2, leaving 88 wt %. This is in good agreement with the 125 wt % maximum capacity of I.sub.2 in ZIF-8, with 100 wt % efficiently contained within the sodalite cages and 25 wt % simply adsorbed to the surface. See D. F. Sava et al., J. Amer. Chem. Soc. 133, 12398 (2011). Impedance spectra and XRD patterns of these evacuated samples were nominally unchanged from before, indicating irreversible structural and electrical responses. Therefore, the sensor can be an integrating sensor whereby the present response is a function of the total dose of the gas absorbed, not the present concentration of the gas in the environment.
[0039] It is hypothesized that the sorption of iodine enables new, faster charge transfer pathways, resulting in significantly lower impedances and R.sub.Z values. Some reports have shown complex, interconnected networks of polyiodides formed in porous organic cages upon sorption of I.sub.2. See T. Hassel et al., J. Amer. Chem. Soc. 133, 14920 (2011). Such a network of I.sub.2/I.sup./I.sub.3.sup. would be expected to significantly decrease the sensor resistance through facile charge transfer pathways. See T. Hassel et al., J. Amer. Chem. Soc. 133, 14920 (2011); and Y.-Q. Hu et al., Chem. Eur. J. 23, 8409 (2017). That such large decreases in resistance are not seen until high I.sub.2 loadings also supports this idea, and is consistent with previous work where it was observed that I.sub.2 was strongly bound in type I sites filled preferentially at low I.sub.2 loadings, followed by less tightly bound I.sub.2 farther out in the pore. See D. F. Sava et al., J. Amer. Chem. Soc. 133, 12398 (2011).
Sensor Response as a Function of Time
[0040] These sensors were successfully used to detect I.sub.2 in real time at room temperature in air. A frequency of 100 mHz was chosen to continuously monitor the impedance and phase angle, with the resulting data plotted in
[0041] Initially, larger changes in impedance can be seen at lower frequencies. Unfortunately, measurement times at lower frequencies start to eclipse the response of the device; measurements at 10 mHz require near 600 s, while those at 100 mHz require no more than 60 s. Optimization of sample geometry, thinning ZIF-8 film thickness from 35 m to <1 m, should increase the sensitivity of the sensor by requiring a lower absolute mass of captured I.sub.2 to create the same impedance response.
[0042] It is worth noting that unlike traditional sensors, which often display a reversible electrical response to a chemical stimulus, the present impedance value of these sensors relates the present I.sub.2 loading in the sensor, and not the environmental level. Thus, this sensor is an integrating sensor that detects whether the sensor has ever been exposed to I.sub.2 in its lifetime. Because of the preferential sorption of I.sub.2 in ZIF-8, it should be possible to detect the presence of I.sub.2 at extremely low concentrations, given a long enough exposure time.
Sensor's Iodine Selectivity Versus Competing Gas Species
[0043] One of the most attractive aspects of using MOFs for chemical sensors is the chemical tunability of the structures and how these influence the selective sorption of various species, minimizing interfering responses. In
[0044] The present invention has been described as a sensor for the direct detection of iodine. It will be understood that the above description is merely illustrative of the applications of the principles of the present invention, the scope of which is to be determined by the claims viewed in light of the specification. Other variants and modifications of the invention will be apparent to those of skill in the art.